Agriculture sulfonamides

ABSTRACT

N-(heterocyclicaminocarbonyl)arylsulfonamides and thienylsulfonamides in which the heterocyclic radical is disubstituted; e.g., N-[[4-(2-methoxyethyoxy)-6-methylpyrimidin-2-yl]aminocarbonyl]-2-nitrobenzenesulfonamide and N-[[4-(2,2,2-trifluoroethoxy)-6-methylpyrimidin-2-yl]aminocarbonyl]-2-nitrobenzenesulfonamide; are useful for the regulation of plant growth and as pre-emergence and post-emergence herbicides.

RELATED APPLICATION

This is a division of application Ser. No. 116,920, filed Jan. 30, 1980, now U.S. Pat. No. 4,501,607, which is a continuation-in-part of my copending patent application U.S. Ser. No. 063,208, filed Aug. 7, 1979 abandoned, which in turn is a continuation-in-part of my copending patent application U.S. Ser. No. 946,176, filed Sept. 27, 1978 U.S. Pat. No. 4,214,890.

BACKGROUND OF THE INVENTION

This invention relates to novel N-(heterocyclicaminocarbonyl)arylsulfonamides and N-(heterocyclicaminocarbonyl)thienylsulfonamides in which the heterocyclic radical is disubstituted. The compounds of this invention and their agriculturally suitable salts, are useful as agricultural chemicals, e.g., plant growth regulants and herbicides.

U.S. application Ser. Nos. 824,805 filed Aug. 15, 1977 and 840,389, filed Oct. 6, 1977 disclose, inter alia, compounds of the following formula as herbicides: ##STR1## In the former R is a radical having the formula: ##STR2## and in the latter, a radical having the formula: ##STR3## In each of those applications, R₁ may be ##STR4## R₃ may be chlorine, bromine, fluorine, nitro, methyl, methoxy, trifluoromethyl or ##STR5##

n is 0, 1 or 2; R₄, R₅, R₆ and R₇ may each be hydrogen, fluorine, chlorine, bromine, or methyl; moreover in each application, each of R₅, R₆ and R₇ may be methoxy. In each application, X may be alkoxy of 1-3 carbon atoms, trifluoromethyl, CH₃ S-- or CH₃ OCH₂ --; Z is methyl or methoxy; and W is oxygen or sulfur.

U.S. application Ser. No. 840,167, filed Oct. 6, 1977, discloses, inter alia, compounds having the following formula as herbicides: ##STR6## wherein each of R₁ and R₂ may be hydrogen or methyl; R₃ is ##STR7## X may be alkoxy of one to three carbons, CF₃, CH₃ S--, CH₃ OCH₂ -- or CH₃ OCH₂ CH₂ O--; Y is CH₃ or OCH₃ ; and Z is CH or N.

U.S. application Ser. No. 910,965, filed May 30, 1978, disclosed, inter alia, compounds of the following formula as herbicides: ##STR8## wherein ##STR9## is an acid, salt, ester or amide radical; R₁ may be ##STR10## R₂ may be hydrogen, chlorine, bromine, fluorine, nitro, methyl, methoxy or methylthio; R₃ is hydrogen, chlorine, bromine or methyl; R₄ and R₅ are independently hydrogen or methyl; W is oxygen or sulfur; X may be methyl or methoxy; Y may be --OCH₂ CF₃, --O(CH₂)₂ OCH₃, --O(CH₂)₂ OC₂ H₅, --O(CH₂)₃ OCH₃, --O(CH₂)₃ OC₂ H₅, --OCH₂ CO₂ CH₃, --OCH₂ CO₂ C₂ H₅, ##STR11## --O(CH₂)₂ CO₂ CH₃, --O(CH₂)₂ CO₂ C₂ H₅ ; --S(CH₂)₂ OCH₃, --S(CH₂)₂ OC₂ H₅, --SCH₂ CO₂ CH₃, --SCH₂ CO₂ C₂ H₅, ##STR12## --S(CH₂)₂ CO₂ CH₃, or S(CH₂)₂ CO₂ C₂ H₅ ; and Z is CH or N.

The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food and fiber needs, such as cotton, rice, corn, wheat, and the like. The current population explosion and concomitant world food and fiber shortage demand improvements in the efficiency of producing these crops. Preventing or minimizing loss of a portion of such valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency. A wide variety of materials useful for killing or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need still exists however, for effective herbicides.

SUMMARY OF THE INVENTION

According to this invention, there are provided novel compounds of Formula I and their agriculturally suitable salts, suitable agricultural compositions containing them and methods of using them as plant growth regulants pre-emergence and post-emergence herbicides, both general and selective: ##STR13## wherein R is ##STR14## R₁ and R₂ are independently H or CH₃ ; R₄ is Cl, Br, F, NO₂, CH₃, OCH₃, CF₃ or R₃ S(O)_(n), where R₃ is C₁ -C₆ alkyl or C₃ -C₄ alkenyl; R₅ is H, Cl, Br, F, CH₃ or --OCH₃ ; n is 0, 1 or 2; W is O or S; X is CH₃ or --OCH₃ ; Y is C₃ -C₄ alkyl; C₂ -C₄ alkyl substituted with CH₃ O; C₂ -C₄ alkyl substituted with 1-3 atoms of Cl, Br or F; C₁ -C₄ alkyl substituted with C₂ H₅ O, CN, CO₂ H, CO₂ CH₃ or CO₂ C₂ H₅ ; CH₂ F; CH₂ Cl, CH₂ Br; C₂ -C₄ alkenyl; C₂ -C₄ alkynyl; SCN; N₃ ; A(CH₂)_(m) A₁ R₇, where m is 2 or 3; R₇ is C₁ -C₃ alkyl; A is O or S; and A₁ is O or S(O)_(n) ; where A₂ and W₁ are independently O or S, and R₁₅ is C₁ -C₃ alkyl, optionally substituted with 1-3 F, Cl or Br, or R₁₅ is N(CH₃)OCH₃ or NR₈ R₉ ; ##STR15## where L is N(CH₃)OCH₃ or NR₈ R₉, where R₈ and R₉ are independently H, CH₃ or C₂ H₅, or L is OR₁₀ where R₁₀ is H or C₁ -C₄ alkyl; NR₁₁ R₁₂ where R₁₁ is H or CH₃ and R₁₂ is C₃ -C₄ alkenyl, C₂ -C₃ alkyl substituted with OCH₃ or OC₂ H₅, cyclopropyl or C₁ -C₂ alkyl substituted with CN, CO₂ CH₃ or CO₂ C₂ H₅ ; OR₁₃ where R₁₃ is C₄ -C₆ alkyl, C₁ -C₄ cyanoalkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, ##STR16## or C₂ -C₄ alkyl substituted with 1-3 atoms of F, Cl or Br; SR₁₄ where R₁₄ is C₁ -C₂ cyanoalkyl, allyl or propargyl; and Z is CH or N; with the provisos:

(a) when Y is OCH₃ CF₃ or

(b) when Y is A--CH₂ --_(m) OR₇ and R₇ is CH₃ or CH₃ CH₂ ; or

(c) when Y is ##STR17## and L is CH₃ O or CH₃ CH₂ O or (d) when Y is ##STR18## and R₁₅ is CH₃ or CH₃ CH₂ then in provisos a, b, c or d, R₄ must be R₃ S(O)_(n), where R₃ is other than CH₃ ; Also provided that:

(e) when either or both of R₁ and R₂ is CH₃, Y cannot be OCH₂ CH₂ OCH₃.

Preferred for reasons of biological activity, or ease of synthesis, or both, are those compounds of Formula I wherein Y is C₁ -C₄ alkyl substituted with CN, CO₂ CH₃, or CO₂ C₂ H₅ ; C₂ -C₄ alkenyl; C₂ -C₄ alkynyl; SCN; N₃ ; A(CH₂)_(m) A₁ R₇, where m is 2 or 3, R₇ is C₁ -C₃ alkyl and A₁ is O or S(O)_(n) ; ##STR19## where A is O or S, and L is N(CH₃)OCH₃ or NR₈ R₉, where R₈ and R₉ are independently H, CH₃ or C₂ H₅, or L is OR₁₀ where R₁₀ is C₁ -C₄ alkyl; NR₁₁ R₁₂ where R₁₁ is H or CH₃ and R₁₂ is C₃ -C₄ alkenyl, C₂ -C₃ alkyl substituted with OCH₃ or OC₂ H₅, or C₁ -C₂ alkyl substituted with CN, CO₂ CH₃ or CO₂ C₂ H₅ ; OR₁₃ where R₁₃ is C₁ -C₄ cyanoalkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, ##STR20## or C₂ -C₄ alkyl substituted with 1-3 atoms of F, Cl or Br; SR₁₄ where R₁₄ is C₁ -C₂ cyanoalkyl, allyl or propargyl.

More preferred in order of increasing activity and/or increasingly favorable cost are:

(1) Compounds of the preferred scope wherein R₁ and R₂ are H and W is O;

(2) Compounds of the more preferred (1) wherein Y is AR₁₆ where R₁₆ is CH₂ CF₃, CH₂ CH₂ OR₁₇, CH(CH₃)CO₂ R₁₇, (CH₂)₃ OR₁₇ or CH₂ CH₂ CO₂ R₁₇, where A is O or S and R₁₇ is CH₃, --C₂ H₅ or i-C₃ H₇ ;

(3) Compounds of the more preferred (2) wherein A is O and R₁₆ is other than CH₂ CH₂ CO₂ R₁₇ ;

(4) Compounds of more preferred (3) wherein R is ##STR21## (5) Compounds of more preferred (4) wherein R₅ is H or Cl; (6) Compounds of more preferred (5) wherein R₄ is Cl or NO₂ ; and

(7) Compounds of more preferred (6) wherein R₅ is H.

Synthesis

As shown in Equation 1, the compounds of Formula I can be prepared by reacting an appropriately substituted sulfonyl isocyanate or isothiocyanate of Formula II with an appropriate 2-aminopyrimidine or 2-amino-1,3,5-triazine of Formula III; R, W, X, Y and Z being as previously defined. ##STR22##

The reaction of Equation 1 is best carried out in inert aprotic organic solvents such as methylene chloride, tetrahydrofuran or acetonitrile, at ambient pressure and temperature. The mode of addition is not critical; however, it is often convenient to add the sulfonyl isocyanate or isothiocyanate II to a stirred suspension of heterocyclic amine III. Since such isocyanates and isothiocyanates usually are liquids, their addition can be easily controlled. The reaction is generally exothermic. In some cases, the desired product is insoluble in the warm reaction medium and crystallizes from it in pure form. Products soluble in the reaction medium are isolated by evaporation of the solvent, trituration of the solid residue with solvents such as 1-chlorobutane or ethyl ether, and filtration.

As shown in Equation 2, the compounds of Formula I, wherein R₁ is H and R₂ is CH₃, can be prepared by reacting an appropriately substituted sulfonyl isocyanate or isothiocyanate of Formula II with an appropriate 2-methylaminopyrimidine or 2-methylamino-1,3,5-triazine of Formula III; R, R₂, W, X, Y and Z being as previously defined. ##STR23## The reaction is carried out as is described for that of Equation 1.

Compounds of Formula I wherein R₁ is methyl, can be prepared by methylation of the salts of compounds of Formula I wherein R₁ is H, as shown in Equation 3; R, R₂, R₁, W, X, Y and Z being as previously defined and M is a metal cation and Q an anion, such as halide or methyl sulfate. ##STR24##

The reaction of Equation 3 is best carried out in aprotic organic solvents such as tetrahydrofuran, dimethylformamide, or dimethylacetamide, at ambient pressure and temperature. Alkylating agents such as dimethyl sulfate, or methyl iodide can be employed. The desired product can be isolated by pouring the reaction mixture into water and filtering off the precipitated solid.

Alternatively, compounds of Formula I wherein R₁ is methyl, can be prepared by the reaction of an appropriately substituted sulfonyl-N-methylcarbamyl chloride of sulfonyl-N-methylcarbamylthioic chloride of Formula IV with an appropriate 2-aminopyrimidine or 2-amino-1,3,5-triazine of Formula III; as shown in Equation 4; R₂, R₁, R, X, Y, W and Z being as previously defined. ##STR25##

The preparation of ureas from amines and carbamyl chlorides or carbamylthioic chlorides is well known to the art. The reaction can best be carried out by adding equivalent amounts of the chloride IV and amine III to an inert organic solvent, such as tetrahydrofuran, xylene, or methylene chloride, in the presence of acid acceptor, such as triethylamine, pyridine, or sodium carbonate employing temperatures from 20°-130°. Soluble products can be isolated by filtering off precipitated salts and concentration of the filtrate. Insoluble products can be filtered off and washed free of salts with water.

The intermediate chlorides IV can be prepared by phosgenation or thiophosgenation of N-methylsulfonamide salts. The sulfonamide salt is added to an excess of phosgene or thiophosgene in an inert organic solvent, such as tetrahydrofuran, toluene, or xylene, whereupon the chloride IV can be isolated or reacted in situ with the amine III after removal of the excess phosgene or thiophosgene.

The synthesis of heterocyclic amine derivatives has been reviewed in "The Chemistry of Heterocyclic Compounds," a series published by Interscience Publ. New York and London. Aminopyrimidines are described by D. J. Brown in "The Pyrimidines," Vol. XVI of the above series.

2-Amino-1,3,5-triazines can be synthesized according to methods described by E. M. Smolin and L. Rapoport in "s-Triazines and Derivatives," Vol. XIII of the same series. 2-Amino-1,3,5-triazines are also conveniently prepared by the methods of K. R. Huffman and F. C. Schaefer in J. Org. Chem. 28, 1812-1815 and 1816-1821 (1963).

The preparation of agriculturally suitable salts of the compounds of Formula I, as well as starting materials and intermediates for said compounds is disclosed in U.S. applications Ser. No. 824,805 filed Aug. 15, 1977 and Ser. No. 840,389 filed Oct. 6, 1977, the contents of which are incorporated herein by reference.

The compounds of this invention and their preparation are further illustrated by the following examples wherein temperatures are given in degrees centigrade.

EXAMPLE 1 N-[[4-(2-methoxyethoxy)-6-methylpyrimidin-2-yl]aminocarbonyl]-2-chlorobenzenesulfonamide

To a dry stirred solution of 18.3 parts of 2-amino-4-(2-methoxyethoxy)-6-methylpyrimidine in 300 parts of methylene chloride at ambient temperature and pressure was added 22 parts of 2-chlorobenzenesulfonylisocyanate. The mixture was stirred for 2 hours and then the methylene chloride was removed under reduced pressure. The resulting solid was triturated with 1-chlorobutane and filtered to yield 35 parts of N-[[4-(2-methoxyethoxy)-6-methylpyrimidine-2-yl]aminocarbonyl]-2-chlorobenzenesulfonamide, m.p. 130°-140° C. The product showed characteristic absorption bands in the infrared spectrum.

By using the procedure of Example 1 with an equivalent amount of appropriate 2-aminopyrimidines or 2-amino-1,3,5-triazines and appropriately substituted benzenesulfonyl isocyanates or isothiocyanates, the compounds of Table 1 can be prepared.

                                      TABLE 1-A                                    __________________________________________________________________________      ##STR26##                                                                     R.sub.4    R.sub.5                                                                             X   Y                m.p. (°C.)                         __________________________________________________________________________     Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        Cl         H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                              160-163                                   Cl         H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                                                     157-160                                   Cl         H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         Cl         H    CH.sub.3                                                                            ##STR27##       178-191                                   Cl         H    CH.sub.3                                                                            ##STR28##       114-122                                   Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                       Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                           103-115                                   Br         H    CH.sub. 3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                               Br         H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         Br         H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                F          H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        F          H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         F          H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                      NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                                                    95-98                                     NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                              192-194                                   NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                                                     155-165                                   NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         NO.sub.2   H    CH.sub.3                                                                            ##STR29##       175-179                                   NO.sub.2   H    CH.sub.3                                                                            ##STR30##                                                 NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.5                       NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5               CH.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                               CH.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         CH.sub.3   H    CH.sub.3                                                                            ##STR31##                                                 CH.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                OCH.sub.3  H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        OCH.sub.3  H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         OCH.sub.3  H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                OCH.sub.3  H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                       CF.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                               CF.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CF.sub.3   H    CH.sub.3                                                                            ##STR32##                                                 CF.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                       SCH.sub.3  H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        SCH.sub.3  H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                          ##STR33## H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          ##STR34## H    CH.sub.3                                                                            ##STR35##                                                  ##STR36## H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                 ##STR37## H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                ##STR38## H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          ##STR39## H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         Cl         5-Cl CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                                                    151-155                                   Cl         5-Cl CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                              162.5-165                                 Cl         5-Cl CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                                                     182-186                                   Cl         5-Cl CH.sub.3                                                                            ##STR40##                                                 Cl         5-Cl CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                      Cl         3-Cl CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                               Cl         5-Br CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        Cl         5-F  CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         Cl         5-CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                Cl         5-OCH.sub.3                                                                         CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         Cl         6-Cl CH.sub.3                                                                           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         Br         5-Br CH.sub.3                                                                            ##STR41##                                                 Cl         5-Cl OCH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         Cl         5-Cl OCH.sub.3                                                                          OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        F          5-F  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                NO.sub.2   5-Cl CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                               NO.sub.2   6-Cl CH.sub.3                                                                           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         NO.sub.2   3-CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                               NO.sub.2   5-OCH.sub.3                                                                         CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3   5-CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                               CH.sub.3   5-Cl CH.sub.3                                                                            ##STR42##                                                 OCH.sub.3  5-OCH.sub.3                                                                         CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        CF.sub.3   5-Cl CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CF.sub.3   5-Cl CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                SCH.sub.3  5-Cl CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                ##STR43## 5-Cl CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                        ##STR44## 5-OCH.sub.3                                                                         CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         Cl         H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                             127-130                                   Cl         H    CH.sub.3                                                                           SCH.sub.2 CO.sub.2 CH.sub.3                                Cl         5-Cl CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                             131-150                                   Cl         5-Cl CH.sub.3                                                                            ##STR45##                                                 Br         H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OCH.sub.3                               F          H    CH.sub.3                                                                           SCH.sub. 2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5               NO.sub.2   H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        NO.sub.2   H    CH.sub.3                                                                           SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         CH.sub.3   H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OCH.sub.3                               OCH.sub.3  H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        CF.sub.3   H    CH.sub.3                                                                            ##STR46##                                                 CF.sub.3   5-Cl CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OCH.sub.3                                ##STR47## H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        Cl         H    OCH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                               Cl         5-Cl OCH.sub.3                                                                          OCH.sub.2 CF.sub.3                                         NO.sub.2   H    OCH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                                CF.sub.3   H    OCH.sub.3                                                                          OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        CH.sub.3   H    OCH.sub.3                                                                          SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        OCH.sub.3  H    OCH.sub.3                                                                          OCH.sub.2 CF.sub.3                                          ##STR48## H    OCH.sub.3                                                                          OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                       Cl         H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                              160-163°                           Cl         Cl   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                              162.5-165°                         Br         H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         F          H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                              192-194°                           CH.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         OCH.sub.3  H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CF.sub.3   H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3 S H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3 SO                                                                               H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3 SO.sub.2                                                                         H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3 CH.sub.2 SO.sub.2                                                                H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                       H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2                                              H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          ##STR49## H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3 (CH.sub.2).sub.4 CH.sub.2 SO.sub.2                                               H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.2CHCH.sub.2 SO.sub.2                                                               H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3 CHCHCH.sub.2 SO.sub.2                                                            H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         Cl         Cl   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         NO.sub.2   Br   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         F          F    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         CH.sub.3   CH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         NO.sub.2   OCH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                         Cl         H    OCH.sub.3                                                                          OCH.sub.2 CF.sub.3                                         NO.sub.2   H    OCH.sub.3                                                                          OCH.sub.2 CF.sub.3                                         Cl         H    CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                 NO.sub.2   H    CH.sub.3 O                                                                          ##STR50##                                                 Cl         H    CH.sub.3                                                                           CH.sub.2CH.sub.2OCH.sub.3                                  NO.sub.2   H    CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                       Cl         H    CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3              NO.sub.2   H    CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 Cl                                       Cl         H    CH.sub.3                                                                           CH.sub.2 CH.sub.2 F                                        NO.sub.2   H    CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 Br                                       Cl         H    CH.sub.3                                                                            ##STR51##                                                 NO.sub.2   H    CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 CH.sub.2 CCl.sub.3                       Cl         H    CH.sub.3                                                                           CH.sub.2 OCH.sub.2 CH.sub.3                                Cl         H    CH.sub.3                                                                           CH.sub.2 CH.sub.2 CO.sub.2 H                               NO.sub.2   H    CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3               Cl         H    CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.2                          CH.sub.3                                                   NO.sub.2   H    CH.sub.3                                                                           CH.sub.2 F                                                 Cl         H    CH.sub.3                                                                           CH.sub.2 Cl                                                NO.sub.2   H    CH.sub.3                                                                           CH.sub.2 Br                                                Cl         H    CH.sub.3                                                                           CHCH.sub.2                                                 NO.sub.2   H    CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                         Cl         H    CH.sub.3                                                                           CH.sub.2 CHCHCH.sub.3                                      Cl         H    CH.sub.3                                                                           CCH                                                        NO.sub.2   H    CH.sub.3                                                                           CCCH.sub.3                                                 Cl         H    CH.sub.3                                                                           CH.sub.2CCCH.sub.3                                         NO.sub.2   H    CH.sub.3                                                                           SCN                                                        Cl         H    CH.sub.3                                                                           N.sub.3          195°                               NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                                                    95-98°                             Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2OCH.sub.3                                                                     103-115°                           Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.3                       NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                           119-125°                           NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2 CH.sub.3              Cl         H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                           127-130°                           Cl         H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2SCH.sub.3                                NO.sub.2   H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                           131-150°                           NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2SOCH.sub.3                               Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2SO.sub.2 CH.sub.3                        Cl         Cl   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                                                    151-155°                           Cl         Cl   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2OCH.sub.3                                                            103-115°                           Cl         Cl   CH.sub.3                                                                            ##STR52##                                                 NO.sub.2   Cl   CH.sub.3                                                                            ##STR53##                                                 Cl         Cl   CH.sub.3                                                                            ##STR54##                                                 NO.sub.2   Cl   CH.sub.3                                                                            ##STR55##                                                 Cl         Cl   CH.sub.3                                                                            ##STR56##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR57##                                                 Cl         H    CH.sub.3                                                                            ##STR58##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR59##                                                 Cl         H    CH.sub.3                                                                            ##STR60##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR61##                                                 Cl         H    CH.sub.3                                                                            ##STR62##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR63##                                                 Cl         H    CH.sub.3                                                                            ##STR64##                                                 NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                                                     155-165°                           Cl         H    CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                                                     157-160°                           Cl         Cl   CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                                                     182-188°                           NO.sub.2   Cl   CH.sub.3                                                                            ##STR65##                                                 Cl         Cl   CH.sub.3                                                                            ##STR66##                                                 NO.sub.2   Cl   CH.sub.3                                                                            ##STR67##                                                 Cl         H    CH.sub.3                                                                            ##STR68##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR69##                                                 Cl         H    CH.sub.3                                                                            ##STR70##       178-191°                           Cl         H    CH.sub.3                                                                            ##STR71##       143-145°                           NO.sub.2   H    CH.sub.3                                                                            ##STR72##       208-210°                           NO.sub.2   H    CH.sub.3                                                                            ##STR73##                                                 Cl         H    CH.sub.3                                                                            ##STR74##       114-123°                           Cl         H    CH.sub.3                                                                            ##STR75##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR76##                                                 Cl         H    CH.sub.3                                                                            ##STR77##                                                 NO.sub.2   H    CH.sub.3                                                                           NHCH.sub.3                                                 Cl         H    CH.sub.3                                                                            ##STR78##                                                 Cl         H    CH.sub.3                                                                            ##STR79##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR80##                                                 Cl         H    CH.sub.3                                                                            ##STR81##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR82##                                                 Cl         H    CH.sub.3                                                                            ##STR83##                                                 NO.sub.2   H    CH.sub.3                                                                            ##STR84##                                                 Cl         H    CH.sub.3                                                                            ##STR85##                                                 NO.sub.2   H    CH.sub.3                                                                           O(CH.sub.2).sub.3 CH.sub.3                                 Cl         H    CH.sub.3                                                                           O(CH.sub.2).sub.4 CH.sub.3                                 NO.sub.2   H    CH.sub.3                                                                           O(CH.sub.2).sub.5 CH.sub.3                                 Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Br                                      NO.sub.2   H    CH.sub.3                                                                            ##STR86##                                                 Cl         H    CH.sub.3                                                                            ##STR87##                                                 NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CN                                               Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CN                                      NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 CN                             Cl         H    CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CN                    NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2CHCH.sub.2                                        Cl         H    CH.sub.3                                                                           OCH.sub.2CHCHCH.sub.3                                      NO.sub.2   H    CH.sub.3                                                                            ##STR88##                                                 Cl         H    CH.sub.3                                                                           SCH.sub.2 CN                                               NO.sub.2   H    CH.sub.3                                                                           SCH.sub.2 CH.sub.2 CN                                      Cl         H    CH.sub.3                                                                           SCH.sub.2CHCH.sub.2                                        NO.sub.2   H    CH.sub.3                                                                           SCH.sub.2CCH                                               NO.sub.2   H    CH.sub.3                                                                           OCH.sub.2CCH                                               Cl         H    CH.sub.3                                                                           OCH.sub.2CCCH.sub.3                                        __________________________________________________________________________

                                      TABLE 1-B                                    __________________________________________________________________________      ##STR89##                                                                     R.sub.4    R.sub.5                                                                            X   Y                m.p. (°C.)                          __________________________________________________________________________     Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                                                    140-146°                            Cl         5-Cl                                                                               CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          Cl         H   CH.sub.3 O                                                                         OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                              glass                                      NO.sub.2   H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                        CH.sub.3   H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                       OCH.sub.3  H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                         SCH.sub.3  H   CH.sub.3                                                                            ##STR90##                                                   ##STR91## H   CH.sub.3                                                                           SCH.sub.2 CO.sub.2 CH.sub.3                                 CF.sub.3   H   CH.sub.3                                                                           S CH.sub.2 CH.sub.2 OCH.sub.3                               F          H   OCH.sub.3                                                                          OCH.sub.2 CF.sub.3                                          Br         H   OCH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                                 ##STR92## H   OCH.sub.3                                                                           ##STR93##                                                  Cl         H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                              158-166°                            Cl         H   OCH.sub.3                                                                          OCH.sub.2 CF.sub.3                                                                              160-163°                            Br         H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          F          H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          NO.sub.2   H   CH.sub.3 O                                                                         OCH.sub.2 CF.sub.3                                                                              160-168°                            CH.sub.3   H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          OCH.sub.3  H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CF.sub.3   H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.3 S H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.3 SO                                                                               H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.3 SO.sub.2                                                                         H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.3 CH.sub.2 SO.sub.2                                                                H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2                                                       H   CH.sub.3                                                                           OCH.sub. 2 CF.sub.3                                         CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2                                              H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                           ##STR94## H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.3 (CH.sub.2).sub.4 CH.sub.2 SO.sub.2                                               H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.2CHCH.sub.2 SO.sub.2                                                               H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.3 CHCHCH.sub.2 SO.sub.2                                                            H   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          Cl         Cl  CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          NO.sub.2   Br  CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          F          F   CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          CH.sub.3   CH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          NO.sub.2   OCH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                          Cl         H   OCH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                                                                    glass                                      Cl         H   CH.sub.3                                                                           OCH.sub.2 CCl.sub.3                                                                             164-167°                            Cl         H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                  NO.sub.2   H   CH.sub.3 O                                                                          ##STR95##                                                  Cl         H   CH.sub.3                                                                           CH.sub.2CH.sub.2OCH.sub.3                                                                       120-130°                            Cl         H   CH.sub.3 O                                                                         OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                           glass                                      Cl         H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3               NO.sub.2   H   CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 Cl                                        Cl         H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 F                                         NO.sub.2   H   CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 Br                                        Cl         H   CH.sub.3                                                                            ##STR96##                                                  NO.sub.2   H   CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 CH.sub.2 CCl.sub.3                        Cl         H   CH.sub.3                                                                           CH.sub.2 OCH.sub.2 CH.sub.3                                 NO.sub.2   H   CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 Cl                                        Cl         H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CO.sub.2 H                                NO.sub.2   H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                Cl         H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.2                          CH.sub.3                                                    NO.sub.2   H   CH.sub.3                                                                           CH.sub.2 F                                                  Cl         H   CH.sub.3                                                                           CH.sub.2 Cl                                                 NO.sub.2   H   CH.sub.3                                                                           CH.sub.2 Br                                                 Cl         H   CH.sub.3                                                                           CHCH.sub.2                                                  NO.sub.2   H   CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                          Cl         H   CH.sub.3                                                                           CH.sub.2 CHCHCH.sub. 3                                      Cl         H   CH.sub.3                                                                           CCH                                                         NO.sub.2   H   CH.sub.3                                                                           CCCH.sub.3                                                  Cl         H   CH.sub.3                                                                           CH.sub.2CCCH.sub.3                                          NO.sub.2   H   CH.sub.3                                                                           SCN                                                         Cl         H   CH.sub.3                                                                           N.sub.3                                                     Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2OCH.sub.3                                                                     140-146°                            Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.3                                                            oil                                        NO.sub.2   H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2 CH.sub.3               Cl         H   CH.sub.3                                                                           SCH.sub.2 CH.sub.2SCH.sub.3                                 NO.sub.2   H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2SOCH.sub.3                                Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                        Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                  132-135°                            Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2OCH.sub.3                                                            54-57°                              Cl         H   CH.sub.3                                                                            ##STR97##                                                  NO.sub. 2  H   CH.sub.3                                                                            ##STR98##                                                  Cl         H   CH.sub.3                                                                            ##STR99##                                                  NO.sub.2   H   CH.sub.3                                                                            ##STR100##                                                 Cl         H   CH.sub.3                                                                            ##STR101##                                                 NO.sub.2   H   CH.sub.3                                                                            ##STR102##                                                 Cl         H   CH.sub.3                                                                            ##STR103##                                                 NO.sub.2   H   CH.sub.3                                                                            ##STR104##                                                 Cl         H   CH.sub.3                                                                            ##STR105##                                                 NO.sub.2   H   CH.sub.3                                                                            ##STR106##                                                 Cl         H   CH.sub.3                                                                            ##STR107##                                                 NO.sub.2   H   CH.sub.3                                                                            ##STR108##                                                 Cl         H   CH.sub.3                                                                            ##STR109##      129-136°                            Cl         H   CH.sub.3                                                                           OCH.sub.2 CO.sub.2 CH.sub.3                                                                     144-147°                            NO.sub.2   H   CH.sub.3                                                                            ##STR110##                                                 Cl         H   CH.sub.3                                                                            ##STR111##                                                 NO.sub.2   H   CH.sub.3                                                                            ##STR112##                                                 Cl         H   CH.sub.3                                                                            ##STR113##                                                 NO.sub.2   H   CH.sub.3 O                                                                          ##STR114##                                                 Cl         H   CH.sub.3 O                                                                          ##STR115##      130-135°                            Cl         H   CH.sub.3 O                                                                          ##STR116##      158-170°                            Cl         H   CH.sub.3                                                                            ##STR117##      76-80°                              Cl         H   CH.sub.3 O                                                                          ##STR118##        92°                               Cl         H   CH.sub.3 O                                                                          ##STR119##                                                 NO.sub.2   H   CH.sub.3 O                                                                          ##STR120##                                                 Cl         H   CH.sub.3 O                                                                          ##STR121##                                                 NO.sub.2   H   CH.sub.3 O                                                                         NHCH.sub.3                                                  Cl         H   CH.sub.3 O                                                                          ##STR122##                                                 Cl         H   CH.sub.3                                                                            ##STR123##                                                 NO.sub.2   H   CH.sub.3                                                                            ##STR124##                                                 Cl         H   CH.sub.3                                                                            ##STR125##                                                 NO.sub.2   H   CH.sub.3                                                                            ##STR126##                                                 Cl         H   OCH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                           glass                                      Cl         H   CH.sub.3                                                                            ##STR127##                                                 NO.sub.2   H   CH.sub.3                                                                            ##STR128##                                                 Cl         H   CH.sub.3                                                                            ##STR129##                                                 NO.sub.2   H   CH.sub.3                                                                           O(CH.sub.2).sub.3 CH.sub.3                                  Cl         H   CH.sub.3                                                                           O(CH.sub.2).sub.4 CH.sub.3                                  NO.sub.2   H   CH.sub.3                                                                           O(CH.sub.2).sub.5 CH.sub.3                                  Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Br                                       NO.sub.2   H   CH.sub.3                                                                            ##STR130##                                                 Cl         H   CH.sub.3                                                                            ##STR131##                                                 NO.sub.2   H   CH.sub.3                                                                           OCH.sub.2 CN                                                Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CN                                                                           118-125°                            NO.sub.2   H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 CN                              Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CN                     NO.sub.2   H   CH.sub.3                                                                           OCH.sub.2CHCH.sub.2                                         Cl         H   CH.sub.3                                                                           OCH.sub.2CHCHCH.sub.3                                       NO.sub.2   H   CH.sub.3                                                                            ##STR132##                                                 Cl         H   CH.sub.3                                                                           SCH.sub.2 CN                                                NO.sub.2   H   CH.sub.3                                                                           SCH.sub.2 CH.sub.2 CN                                       Cl         H   CH.sub.3                                                                           SCH.sub.2CHCH.sub.2                                         NO.sub.2   H   CH.sub.3                                                                           SCH.sub.2CCH                                                NO.sub.2   H   CH.sub.3                                                                           OCH.sub.2CCH                                                Cl         H   CH.sub.3                                                                           OCH.sub.2CCCH.sub.3                                         Cl         H   CH.sub.3 O                                                                         CH.sub.2 CH.sub.2 OCH.sub.3                                                                     100-107°                            CF.sub.3   H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.3                                                                     130-133°                            Cl         H   CH.sub.3                                                                           SCH.sub.2 CO.sub.2 CH.sub.3                                                                     148-151°                            Cl         H   CH.sub.3 O                                                                         SCH.sub.2 CO.sub.2 CH.sub.3                                                                     78-98°                              Cl         H   CH.sub.3 O                                                                          ##STR133##      150-155°                            Cl         H   CH.sub.3                                                                            ##STR134##      oil                                        Cl         H   CH.sub.3 O                                                                          ##STR135##      130-135°                            Cl         H   CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Cl                                                                           131-142°                            __________________________________________________________________________

                  TABLE 1-C                                                        ______________________________________                                          ##STR136##                                                                    R.sub.4 R.sub.5  X         Y                                                   ______________________________________                                         Cl      H        CH.sub.3  OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                 Cl      H        CH.sub.3  OCH.sub.2 CF.sub.3                                  Cl      5-Cl     CH.sub.3  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                  Cl      5-Cl     CH.sub.3                                                                                  ##STR137##                                         NO.sub.2                                                                               H        CH.sub.3  OCH.sub.2 CH.sub.2 OCH.sub.3                        NO.sub.2                                                                               H        CH.sub.3  OCH.sub.2 CF.sub.3                                  Br      H        OCH.sub.3 SCH.sub.2 CO.sub.2 CH.sub.3                         CH.sub.3                                                                               H        OCH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5        ______________________________________                                    

                  TABLE 1-D                                                        ______________________________________                                          ##STR138##                                                                    R.sub.4   R.sub.5  X         Y                                                 ______________________________________                                         Cl        H        CH.sub.3  OCH.sub.2 CH.sub.2 OCH.sub.3                      Cl        H        CH.sub.3  OCH.sub.2 CF.sub.3                                Cl        5-Cl     CH.sub.3  OCH.sub.2 CO.sub.2 CH.sub.3                       NO.sub.2  H        CH.sub.3                                                                                  ##STR139##                                       NO.sub.2  H        CH.sub.3  SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5               NO.sub.2  H        CH.sub.3  OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5               NO.sub.2  H        OCH.sub.3 OCH.sub.2 CF.sub.3                                Br        H        CH.sub.3  OCH.sub.2 CH.sub.2 OCH.sub.3                      SCH.sub.3 H        OCH.sub.3                                                                                 ##STR140##                                        ##STR141##                                                                              H        OCH.sub.3 S CH.sub.2 CO.sub.2 C.sub.2 H.sub.5               ______________________________________                                    

Example 2 Methyl [6-methyl-2-[(2-thienylsulfonyl)aminocarbonylamino]pyrimidin-4-yloxy]acetate

To a dry stirred solution of 18 parts of methyl (2-amino-6-methylpyrimidin-4-yloxy)acetate in 300 parts of methylene chloride at ambient temperature was added 20 parts of 2-thiophenesulfonylisocyanate. The solution was allowed to stand for 3 hours and was then poured onto ice. The pH of the aqueous layer was adjusted to 11 with sodium hydroxide solution and the methylene chloride layer was separated therefrom. The aqueous layer was neutralized with aqueous hydrochloric acid and then extracted with methylene chloride. The extract was dried and stripped of solvent to yield 8 parts of methyl [6-methyl-2-[(2-thienylsulfonyl)aminocarbonylamino]pyrimidin-4-yloxy]acetate, m.p. 114°-120°.

By using the procedure of Example 2 with equivalent amounts of appropriate 2-aminopyrimidines or 2-amino-1,3,5-triazines and 2-thiophenesulfonylisocyanates or isothiocyanates, the compounds of Table 2 can be prepared.

                  TABLE 2-A                                                        ______________________________________                                          ##STR142##                                                                    X               Y                                                              ______________________________________                                         CH.sub.3        OCH.sub.2 CH.sub.2 OCH.sub.3                                   CH.sub.3        OCH.sub.2 CF.sub.3                                             CH.sub.3                                                                                        ##STR143##                                                    CH.sub.3        OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                    CH.sub.3        OCH.sub.2 CH.sub.2 OCH.sub.3                                   CH.sub.3        SCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                          CH.sub.3        SCH.sub.2 CO.sub.2 CH.sub.3                                    OCH.sub.3       OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                            OCH.sub.3       OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                          ______________________________________                                    

                  TABLE 2-B                                                        ______________________________________                                          ##STR144##                                                                    X                Y                                                             ______________________________________                                         CH.sub.3         OCH.sub.2 CH.sub.2 OCH.sub.3                                  CH.sub.3         OCH.sub.2 CF.sub.3                                            CH.sub.3         OCH.sub.2 CO.sub.2 CH.sub.3                                   CH.sub.3                                                                                         ##STR145##                                                   OCH.sub.3        OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                          OCH.sub.3        OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           OCH.sub.3        OCH.sub.2 CF.sub.3                                            CH.sub.3         OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                            CH.sub.3         SCH.sub.2 CH.sub.2 OCH.sub.3                                  CH.sub.3         SCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                          ______________________________________                                    

                  TABLE 2-C                                                        ______________________________________                                          ##STR146##                                                                    X                Y                                                             ______________________________________                                         CH.sub.3         OCH.sub.2 CH.sub.2 OCH.sub.3                                  CH.sub.3         OCH.sub.2 CF.sub.3                                            CH.sub.3         OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                            CH.sub.3                                                                                         ##STR147##                                                   CH.sub.3         OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                   CH.sub.3         OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           OCH.sub.3        OCH.sub.2 CO.sub.2 CH.sub.3                                   OCH.sub.3        OCH.sub.2 CF.sub.3                                            OCH.sub.3        OCH.sub.2 CH.sub.2 OCH.sub.3                                  OCH.sub.3        SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           CH.sub.3         SCH.sub.2 CO.sub.2 CH.sub.3                                   ______________________________________                                    

                  TABLE 2-D                                                        ______________________________________                                          ##STR148##                                                                    X                Y                                                             ______________________________________                                         CH.sub.3         OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           CH.sub.3         OCH.sub.2 CF.sub.3                                            CH.sub.3                                                                                         ##STR149##                                                   OCH.sub.3        OCH.sub.2 CF.sub.3                                            OCH.sub.3        OCH.sub.2 CO.sub.2 CH.sub.3                                   OCH.sub.3        SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           OCH.sub.3        SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                            CH.sub.3                                                                                         ##STR150##                                                   CH.sub.3         SCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                          ______________________________________                                    

By using the procedure of Equation 2 with an equivalent amount of appropriate 2-methylaminopyrimidines or 2-methylamino-1,3,5-triazines and appropriately substituted benzenesulfonylisocyanates or isothiocyanates, the compounds of Table 3 can be prepared. For example, to a dry stirred solution of 19.7 parts of 2-methylamino-4-(2-methoxyethylthio)-6-methylpyrimidine in 300 parts of methylene chloride at ambient temperature is added 22.8 parts of 2-nitrobenzenesulfonylisocyanate. That mixture is stirred and refluxed for 4 hours, and then the methylene chloride is removed under reduced pressure. The resulting solid is triturated with 1-chlorobutane to yield N-[N-[4-(2-methoxyethylthio)-6-methylpyrimidin-2-yl]-N-methylaminocarbonyl]-2-nitrobenzenesulfonamide.

                  TABLE 3-A                                                        ______________________________________                                          ##STR151##                                                                    R.sub.4   R.sub.5  X         Y                                                 ______________________________________                                         Cl        H        CH.sub.3  SCH.sub.2 CH.sub.2 OCH.sub.3                      Cl        H        CH.sub.3  OCH.sub.2 CF.sub.3                                Cl        5-Cl     CH.sub.3  OCH.sub.2 CO.sub.2 CH.sub.3                       NO.sub.2  H        CH.sub.3  OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5       NO.sub.2  H        OCH.sub.3 SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5               Br        H        CH.sub.3  SCH.sub.2 CO.sub.2 CH.sub.3                       CH.sub.3  H        CH.sub.3                                                                                  ##STR152##                                       ______________________________________                                    

                  TABLE 3-B                                                        ______________________________________                                          ##STR153##                                                                    R.sub.4   R.sub.5  X         Y                                                 ______________________________________                                         Cl        H        CH.sub.3  SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5               Cl        H        CH.sub.3  OCH.sub.2 CF.sub.3                                Cl        5-Cl     CH.sub.3  SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5               NO.sub.2  H        CH.sub.3  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                Br        H        CH.sub.3  OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3              OCH.sub.3 H        OCH.sub.3 OCH.sub.2 CF.sub.3                                ______________________________________                                    

                  TABLE 3-C                                                        ______________________________________                                          ##STR154##                                                                    R.sub.4  R.sub.5  X         Y                                                  ______________________________________                                         Cl       H        CH.sub.3  SCH.sub.2 CH.sub.2 OCH.sub.3                       Cl       H        CH.sub.3  OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                 Cl       5-Cl     CH.sub.3  OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3              NO.sub.2 H        CH.sub.3  OCH.sub.2 CF.sub.3                                 NO.sub.2 H        OCH.sub.3 OCH.sub.2 CF.sub.3                                 ______________________________________                                    

                  TABLE 3-D                                                        ______________________________________                                          ##STR155##                                                                    R.sub.4  R.sub.5  X         Y                                                  ______________________________________                                         Cl       H        CH.sub.3  OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                Cl       H        CH.sub.3                                                                                  ##STR156##                                        Cl       5-Cl     OCH.sub.3 OCH.sub.2 CF.sub.3                                 NO.sub.2 H        CH.sub.3  SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                NO.sub.2 H        OCH.sub.3 OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5        Br       H        CH.sub.3  OCH.sub.2 CF.sub.3                                 ______________________________________                                    

EXAMPLE 3 N-[N-[4-(2,2,2-Trifluoroethoxy)-6-methylpyrimidin-2-yl]-N-methylaminocarbonyl]-2-thiophenesulfonamide

To a dry stirred solution of 22.1 parts of 2-methylamino-4-(2,2,2-trifluorethoxy)-6-methylpyrimidine in 250 parts of methylene chloride at ambient temperature was added 18.9 parts of 2-thiophenesulfonyl isocyanate. That mixture was stirred and refluxed for 2 hours. The methylene chloride was removed under reduced pressure, and the resulting solid was triturated with toluene to yield 19 parts of N-[N-[4-(2,2,2-trifluoroethoxy)-6-methylpyrimidin-2-yl]-N-methylaminocarbonyl]-2-thiophenesulfonamide.

By using the procedure of Example 3 with equivalent amounts of appropriate 2-methylaminopyrimidines or 2-methylamino-1,3,5-triazines and 2-thiophenesulfonyl isocyanates or isothiocyanates, the compounds of Table 4 can be prepared.

                  TABLE 4-A                                                        ______________________________________                                          ##STR157##                                                                    X                Y                                                             ______________________________________                                         CH.sub.3         SCH.sub.2 CH.sub.2 OCH.sub.3                                  CH.sub.3         OCH.sub.2 CO.sub.2 CH.sub.3                                   CH.sub.3         OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                          CH.sub.3         SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           OCH.sub.3        OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           OCH.sub.3        OCH.sub.2 CF.sub.3                                            OCH.sub.3                                                                                        ##STR158##                                                   ______________________________________                                    

                  TABLE 4-B                                                        ______________________________________                                          ##STR159##                                                                    X               Y                                                              ______________________________________                                         CH.sub.3        OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                            CH.sub.3        OCH.sub.2 CF.sub.3                                             CH.sub.3        OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                          OCH.sub.3       SCH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                   OCH.sub.3       SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                             ______________________________________                                    

                  TABLE 4-C                                                        ______________________________________                                          ##STR160##                                                                    X                Y                                                             ______________________________________                                         CH.sub.3         SCH.sub.2 CH.sub.2 OCH.sub.3                                  CH.sub.3         OCH.sub.2 CF.sub.3                                            CH.sub.3         OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                          OCH.sub.3        SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           ______________________________________                                    

                  TABLE 4-D                                                        ______________________________________                                          ##STR161##                                                                    X                 Y                                                            ______________________________________                                         CH.sub.3                                                                                          ##STR162##                                                  CH.sub.3          SCH.sub.2 CO.sub.2 CH.sub.3                                  CH.sub.3          SCH.sub.2 CH.sub.2 OCH.sub.3                                 OCH.sub.3         OCH.sub.2 CF.sub.3                                           ______________________________________                                    

N-methyl compounds of this invention can be prepared in accordance with the procedures described above. For example, the methylation procedure of Equation 3 can be used as follows:

An equivalent amount of sodium hydride (50% mineral oil dispersion) is added to a solution of N-[[4-(2-methoxyethylthio)-6-methylpyrimidin-2-yl]aminocarbonyl]-2,5-dichlorobenzenesulfonamide in dimethylformamide under a nitrogen atmosphere. After hydrogen evolution ceases, an equivalent amount of dimethylsulfate is added. After stirring for 12 hours the reaction mixture is poured into a large volume of water. The resulting precipitate is filtered to yield N-[[4-(2-methoxyethylthio)-6-methylpyrimidin-2-yl]aminocarbonyl]-2,5-dichloro-N-methylbenzenesulfonamide.

Likewise, compounds of this invention wherein both of the urea nitrogens are methylated can be prepared by the procedure of Equation 4 as follows:

To 18 parts of N-[(2-chlorophenyl)sulfonyl]N-methylcarbamyl chloride in 300 parts of tetrahydrofuran containing 10 parts of triethylamine is added 22 parts of 2-methylamino-4-(2,2,2-trifluoroethoxy)-6-methylpyrimidine. After stirring at reflux for 10 hours, the precipitated salts are filtered off and the filtrate is concentrated to yield N-[N-[4-(2,2,2,-trifluoroethoxy)-6-methylpyrimidin-2-yl]-N-methylaminocarbonyl]-2-chloro-N-methylbenzenesulfonamide.

By using an appropriate N-heterocyclic-N-aminocarbonylbenzenesulfonamide in the foregoing methylation procedure, the compounds of Table 5 can be prepared. Alternatively, by using an appropriate carbamylchloride and an appropriate methylaminoheterocycle with the above-described procedure, the compounds of Table 5 can be prepared.

                  TABLE 5-A                                                        ______________________________________                                          ##STR163##                                                                    R.sub.2 R.sub.4 R.sub.5 X      Y                                               ______________________________________                                         H       Cl      H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OCH.sub.3                    H       Cl      H       CH.sub.3                                                                              OCH.sub.2 CF.sub.3                              H       Cl      H       CH.sub.3                                                                              OCH.sub.2 CO.sub.2 CH.sub.3                     H       Cl      5-Cl    CH.sub.3                                                                              OCH.sub.2 CH.sub.2 CO.sub.2 C.sub.2                                            H.sub.5                                         H       NO.sub.2                                                                               H       CH.sub.3                                                                              OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5             H       NO.sub.2                                                                               H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5             H       NO.sub.2                                                                               H       CH.sub.3                                                                               ##STR164##                                     H       NO.sub.2                                                                               H       OCH.sub.3                                                                             SCH.sub.2 CO.sub.2 CH.sub.3                     H       Br      5-Cl    OCH.sub.3                                                                             OCH.sub.2 CF.sub.3                              CH.sub.3                                                                               CH.sub.3                                                                               H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OCH.sub.3                    CH.sub.3                                                                               Cl      H       CH.sub.3                                                                              OCH.sub.2 CO.sub.2 CH.sub.3                     CH.sub.3                                                                               Cl      5-Cl    OCH.sub.3                                                                             OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5             CH.sub.3                                                                               NO.sub.2                                                                               H       CH.sub.3                                                                              OCH.sub.2 CF.sub.3                              CH.sub.3                                                                               NO.sub.2                                                                               H       CH.sub.3                                                                               ##STR165##                                     ______________________________________                                    

                  TABLE 5-B                                                        ______________________________________                                          ##STR166##                                                                    R.sub.2                                                                              R.sub.4   R.sub.5 X      Y                                               ______________________________________                                         H     Cl        H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OCH.sub.3                    H     Cl        5-Cl    CH.sub.3                                                                              OCH.sub.2 CF.sub.3                              H     NO.sub.2  H       CH.sub.3                                                                              OCH.sub.2 CO.sub.2 CH.sub.3                     H     NO.sub.2  H       CH.sub.3                                                                              SCH.sub.2 CO.sub.2 CH.sub.3                     H     NO.sub.2  H       OCH.sub.3                                                                              ##STR167##                                     CH.sub.3                                                                             OCH.sub.3 H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OCH.sub.3                    CH.sub.3                                                                             SCH.sub.3 H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5             CH.sub.3                                                                              ##STR168##                                                                              H       OCH.sub.3                                                                             OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3           CH.sub.3                                                                             NO.sub.2  H       CH.sub.3                                                                              OCH.sub.2 CF.sub.3                              ______________________________________                                    

By using an appropriately substituted N-methyl-N-methylsulfonylthiocarbamyl chloride and an appropriately substituted 2-aminopyrimidine or 2-amino-1,3,5-triazine the compounds of Table 6 can be made in accordance with the procedure exemplified above.

                  TABLE 6-A                                                        ______________________________________                                          ##STR169##                                                                    R.sub.2                                                                               R.sub.4  R.sub.5 X      Y                                               ______________________________________                                         H      Cl       H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OCH.sub.3                    H      Cl       5-Cl    CH.sub.3                                                                              OCH.sub.2 CF.sub.3                              H      NO.sub.2 H       CH.sub.3                                                                              OCH.sub.2 CO.sub.2 CH.sub.3                     H      NO.sub.2 H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OCH.sub.3                    H      CH.sub.3 H       CH.sub.3                                                                              SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5              H      OCH.sub.3                                                                               H       OCH.sub.3                                                                              ##STR170##                                     CH.sub.3                                                                              Br       H       CH.sub.3                                                                              OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5             CH.sub.3                                                                              Cl       5-Cl    CH.sub.3                                                                               ##STR171##                                     CH.sub.3                                                                              NO.sub.2 H       CH.sub.3                                                                              OCH.sub.2 CF.sub.3                              CH.sub.3                                                                              NO.sub.2 H       OCH.sub.3                                                                             OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3           ______________________________________                                    

                  TABLE 6-B                                                        ______________________________________                                          ##STR172##                                                                    R.sub.2                                                                               R.sub.4  R.sub.5 X      Y                                               ______________________________________                                         CH.sub.3                                                                              Cl       H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OCH.sub.3                    CH.sub.3                                                                              Cl       5-Cl    CH.sub.3                                                                              OCH.sub.2 CO.sub.2 CH.sub.3                     CH.sub.3                                                                              NO.sub.2 H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 OCH.sub.3                    CH.sub.3                                                                              NO.sub.2 H       CH.sub.3                                                                              SCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3            CH.sub.3                                                                              CH.sub.3 H       OCH.sub.3                                                                              ##STR173##                                     H      Br       H       CH.sub.3                                                                              OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5             H      Cl       5-Cl    CH.sub.3                                                                              OCH.sub.2 CF.sub.3                              H      NO.sub.2 H       CH.sub.3                                                                              OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3           H      SCH.sub.3                                                                               H       OCH.sub.3                                                                             SCH.sub. 2 CO.sub.2 C.sub.2 H.sub.5             ______________________________________                                    

The compounds of Table 7 can be prepared by the aforesaid methylation reaction by using an appropriate N-[(1,3,5-triazin-2-yl)aminocarbonyl]-2-thiophenesulfonamide; N-[(pyrimidin-2-yl)aminocarbonyl]-2-thiophenesulfonamide; N-[(1,3,5-triazin-2-yl)aminothioxomethyl]-2-thiophenesulfonamide or N-[(pyrimidin-2-yl)aminothioxomethyl]-2-thiophenesulfonamide. Alternatively, the compounds of Table 7 can be prepared in acordance with the above-exemplified procedure, using an appropriately substituted N-methyl-N-(2-thienylsulfonyl)carbamyl chloride or thiocarbamyl chloride and an appropriately substituted 2-aminopyrimidine or 2-amino-1,3,5-triazine.

                  TABLE 7-A                                                        ______________________________________                                          ##STR174##                                                                    R.sub.2    X          Y                                                        ______________________________________                                         H          CH.sub.3   SCH.sub.2 CH.sub.2 OCH.sub.3                             H          CH.sub.3   OCH.sub.2 CF.sub.3                                       H          OCH.sub.3  OCH.sub.2 CO.sub.2 CH.sub.3                              H          OCH.sub.3  SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                      H          CH.sub.3   OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                    CH.sub.3   CH.sub.3                                                                                   ##STR175##                                              CH.sub.3   CH.sub.3   OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                     CH.sub.3   CH.sub.3   OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                      CH.sub.3   CH.sub.3   OCH.sub.2 CF.sub.3                                       ______________________________________                                    

                  TABLE 7-B                                                        ______________________________________                                          ##STR176##                                                                    R.sub.2    X           Y                                                       ______________________________________                                         H          CH.sub.3    SCH.sub.2 CH.sub.2 OCH.sub.3                            H          CH.sub.3    OCH.sub.2 CF.sub.3                                      H          CH.sub.3    SCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2                   H          OCH.sub.3   OCH.sub.2 CO.sub.2 CH.sub.3                             H          OCH.sub.3   SCH.sub.2 CO.sub.2 CH.sub.3                             CH.sub.3   OCH.sub.3                                                                                   ##STR177##                                             CH.sub.3   CH.sub.3    OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                    CH.sub.3   CH.sub.3    SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                     CH.sub.3   CH.sub.3                                                                                    ##STR178##                                             CH.sub.3   CH.sub.3    OCH.sub.2 CF.sub.3                                      ______________________________________                                    

                  TABLE 7-C                                                        ______________________________________                                          ##STR179##                                                                    R.sub.2    X           Y                                                       ______________________________________                                         H          CH.sub.3    OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                     H          CH.sub.3    OCH.sub.2 CF.sub.3                                      H          CH.sub.3                                                                                    ##STR180##                                             H          OCH.sub.3   OCH.sub.2 CF.sub.3                                      H          CH.sub.3    OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                    H          CH.sub.3    SCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                   CH.sub.3   CH.sub.3    SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                     CH.sub.3   CH.sub.3    SCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                    CH.sub.3   OCH.sub.3   SCH.sub.2 CH.sub.2 OCH.sub.3                            CH.sub.3   OCH.sub.3   OCH.sub.2 CF.sub.3                                      ______________________________________                                    

                  TABLE 7-D                                                        ______________________________________                                          ##STR181##                                                                    R.sub.2    X           Y                                                       ______________________________________                                         H          CH.sub.3    SCH.sub.2 CH.sub.2 OCH.sub.3                            H          OCH.sub.3   OCH.sub.2 CF.sub.3                                      H          CH.sub.3    OCH.sub.2 CO.sub.2 CH.sub.3                             CH.sub.3   CH.sub.3    SCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                     CH.sub.3   OCH.sub.3   SCH.sub.2 CO.sub.2 CH.sub.3                             CH.sub.3   CH.sub.3    OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3                   CH.sub.3   CH.sub.3                                                                                    ##STR182##                                             ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of them can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are used primarily as concentrates which are to be diluted prior to ultimate use. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in the approximate proportions set forth in Table 8.

                  TABLE 8                                                          ______________________________________                                                        Weight Percent*                                                                Active            Surfac-                                                      Ingredient                                                                             Diluent(s)                                                                               tant(s)                                       ______________________________________                                         Wettable Powders 20-90      0-74     1-10                                      Oil Suspensions,  5-50     40-95     0-15                                      Emulsions                                                                      (including                                                                     Emulsifiable                                                                   Concentrates)                                                                  Aqueous Suspensions                                                                             10-50     40-84     1-20                                      Dusts             1-25     70-99     0-5                                       Granules and Pellets                                                                            0.1-95      5-99.9  0-15                                      High Strength Compositions                                                                      90-99      0-10     0-2                                       ______________________________________                                          *Active Ingredient plus at least one of a Surfactant or a Diluent equals       100 weight percent.                                                      

Lower or higher levels of active ingredient can be present, depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation, or by tank mixing.

Some typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well know. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending, and usually grinding, as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets can be made by spraying the active material on preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pp. 8-59ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, 169-182.

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4.

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

Unless indicated otherwise, all parts are by weight in the following examples.

EXAMPLE 4

    ______________________________________                                         Wettable Powder:                                                               ______________________________________                                         N--[[4-(2,2,2-trifluoroethoxy)-6-methylpyrimidin-                                                         90%                                                 2-yl]aminocarbonyl]-2-nitrobenzenesulfonamide                                  dioctyl sodium sulfosuccinate                                                                             0.1%                                                sodium ligninsulfonate     1%                                                  synthetic fine silica      8.9%                                                ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce particles almost all of which are below 100 microns in size. That material is shifted through a U.S.S. No. 50 screen and packaged.

EXAMPLE 5

    ______________________________________                                         Granule                                                                        ______________________________________                                         wettable powder of Example 4                                                                        10%                                                       attapulgite granules 90%                                                       (U.S.S.#20-40; 0.84-0.42 mm)                                                   ______________________________________                                    

A slurry of wettable powder containing 50% solids is sprayed onto the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

EXAMPLE 6

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N--[[4-(2-methoxyethoxy)-6-methylpyrimidin-2-yl]-                                                         40%                                                 aminocarbonyl]-2-nitrobenzenesulfonamide                                       dioctyl sodium sulfosuccinate                                                                             1.5%                                                sodium ligninsulfonate     3%                                                  low viscosity methyl cellulose                                                                            1.5%                                                attapulgite                54%                                                 ______________________________________                                    

The ingredients are thoroughly blended and passed through an air mill to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 59 sieve (0.3 mm opening) before packaging.

EXAMPLE 7

    ______________________________________                                         Granule                                                                        ______________________________________                                         wettable powder of Example 6                                                                        25%                                                       gypsum               64%                                                       potassium sulfate    11%                                                       ______________________________________                                    

The ingredients are blended in a rotating mixer, and water is sprayed onto that blend so as to effect granulation. When most of the granules have reached 1.0 to 0.42 mm (U.S.S. #18 to 40 sieves) in size, they are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. The resulting granules contain 10% of the active ingredient.

EXAMPLE 8

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N--[[4-(2,2,2-trifluoroethoxy)-6-methylpyrimidin-                                                         80%                                                 2-yl]aminocarbonyl]-2-nitrobenzenesulfonamide                                  sodium alkylnaphthalenesulfonate                                                                           2%                                                 sodium ligninsulfonate      2%                                                 synthetic amorphorus silica                                                                                3%                                                 kaolinite                  13%                                                 ______________________________________                                    

The ingredients are thoroughly blended after grinding in a hammer mill to produce particles essentially all of which are under 100 microns in size; the material is reblended, sifted through a U.S.S. No. 50 sieve and packaged.

EXAMPLE 9

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N--[[4-(2-methoxyethoxy)-6-methylpyrimidin-2-yl]-                                                         65%                                                 aminocarbonyl]-2-nitrobenzenesulfonamide                                       dodecylphenol polyethylene glycol ether                                                                    2%                                                 sodium ligninsulfonate      4%                                                 sodium silicoaluminate      6%                                                 montmorillonite (calcined) 23%                                                 ______________________________________                                    

The ingredients are thoroughly blended. The liquid surfactant is added by spraying on the solid ingredients in a blender. After grinding in a hammer mill to produce particles almost all of which are below 100 microns in size, the material is reblended, sifted through a U.S.S. #50 sieve (0.3 mm opening) and packaged.

EXAMPLE 10

    ______________________________________                                         Oil Suspension                                                                 ______________________________________                                         N--[[4-(2,2,2-trifluoroethoxy)-6-methylpyrimidin-                                                         25%                                                 2-yl]aminocarbonyl]-2-nitrobenzenesulfonamide                                  polyoxyethylene sorbitol hexaoleate                                                                        5%                                                 highly aliphatic hydrocarbon oil                                                                          70%                                                 ______________________________________                                    

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting suspension may be applied directly, but preferably after being extended further with oils or emulsified in water.

EXAMPLE 11

    ______________________________________                                         Aqueous Suspension                                                             ______________________________________                                         N--[[4-(2-methoxyethoxy)-6-methylpyrimidin-2-yl]-                                                         25%                                                 aminocarbonyl]-2-nitrobenzenesulfonamide                                       hydrated attapulgite       3%                                                  crude calcium ligninsulfonate                                                                             10%                                                 sodium dihydrogen phosphate                                                                               0.5%                                                water                      61.5%                                               ______________________________________                                    

The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to sizes under 10 microns, and then packaged.

EXAMPLE 12

    ______________________________________                                         Extruded Pellet                                                                ______________________________________                                         N--[[4-(2,2,2-trifluoroethoxy)-6-methylpyrimidin-                                                         25%                                                 2-yl]aminocarbonyl]-2-nitrobenzenesulfonamide                                  anhydrous sodium sulfate   10%                                                 crude calcium ligninsulfonate                                                                              5%                                                 sodium alkylnaphthalenesulfonate                                                                           1%                                                 calcium/magnesium bentonite                                                                               59%                                                 ______________________________________                                    

The ingredients are blended, hammer milled and then moistened with about 12% water. The mixture is extruded in the form of cylinders about 3 mm in diameter which are cut to produce pellets about 3 mm long. The pellets may be used directly, after drying, or dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

EXAMPLE 13

    ______________________________________                                         Solution                                                                       ______________________________________                                         N--[[4-(2,2,2-trifluoroethoxy)-6-methylpyrimidin-                                                          5%                                                 2-yl]aminocarbonyl]-2-nitrobenzenesulfonamide                                  dimethylformamide          95%                                                 ______________________________________                                    

The ingredients are combined and stirred to produce a solution, which can be used for low volume applications.

UTILITY

The compounds of the present invention are highly active herbicides. They have utility for broad spectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, oil well sites, drive-in theatres, parking lots, billboards, highway and railroad structures. By properly selecting rate and time of application, compounds of this invention may be used also to modify plant growth beneficially.

The precise amount of the compound of Formula I to be used in any given situation will vary according to the particular end result desired, the amount of foliage present, the weeds to be controlled, the soil type, the formulation and mode of application, weather conditions, etc. Since so many variables play a role, it is not possible to state a rate of application suitable for all situations. Broadly speaking, the compounds of this invention are used at levels of about 0.005 to 20 kg/ha with a preferred range of 0.125 to 10 kg/ha. In general, the higher rates of application from within this range will be selected for adverse conditions or where extended persistence in soil is desired.

The compounds of Formula I may be combined with other herbicides and are particularly useful in combination with ureas, such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, and 1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea; the triazines such as 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine; the uracils such as 5-bromo-3-sec-butyl-6-methyluracil; N-(phospono-methyl)glycine; 3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, N,N-dimethyl-2,2-diphenylacetamide; 2,4-dichlorophenoxyacetic acid (and closely related compounds); 4-chloro-2-butynyl-3-3-chlorophenylcarbamate; diisopropylthiolcarbamic acid, ester with 2,3-dichloroallyl alcohol; diisopropylthiolcarbamic acid, S-(2,3,3-trichloroallyl)ester; ethyl-N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate, 1,2-dimethyl-3,5-diphenylpyrazolium methylsulfate; methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate; 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one; 3-isopropyl-1H-2,1,3-benzothiodiazin(4H)-3H-one 2,2-dioxide; α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine; 1,1'-dimethyl-4,4'-bipyridinium ion; monosodium methanearsonate; and 2-chloro-2',6'-diethyl(methoxymethyl)acetanilide.

The activity of the compounds of this invention was discovered in greenhouse tests. The tests are described and the data resulting from them are shown below.

0=no effect

10=maximum effect

B=burn

C=chlorosis or necrosis

D=defoliation

E=emergence inhibition

G=growth retardation

H=formative effects

S=albinism

U=unusual pigmentation

6Y=abscised buds or flowers

TEST PROCEDURE A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory (Ipomoea spp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice, and wheat, as well as nutsedge tubers (Cyperus rotundus), were planted in a growth medium and treated preemergence with a nonphytotoxic solvent solution of the compounds of Table 9. Other batches of seeds and tubers for all of the foregoing weed and crop plants were planted at the same time as controls. The control plantings were untreated; i.e., neither any compound nor any solvent was applied. At the same time, cotton having five leaves (including cotyledonary ones), bush beans with the third trifoliate leaf expanding, crabgrass with two leaves, barnyardgrass with two leaves, wild oats with two leaves, cassia with three leaves (including cotyledonary ones), morningglory with four leaves (including the cotyledonary ones), cocklebur with four leaves (including the cotyledonary ones), sorghum with four leaves, corn with four leaves, soybean with two cotyledonary leaves, rice with three leaves, wheat with one leaf, and nutsedge with three-five leaves were sprayed with a nonphytotoxic solvent solution of the compounds of Table 9. Other groups of all the same weed and crop plants were sprayed with the same nonphytotoxic solvent so as to provide control plants. Preemergence and postemergence treated plants and controls were maintained in a greenhouse for sixteen days, then all treated plants were compared with their respective controls and rated visually for response to treatment. The data in Table 9 indicate that certain of the compounds of this invention have utility for selective post-emergence weed control in wheat.

    TABLE 9       Post-Emergence   Bush  Morning Cock-  Nut- Crab- Barnyard Wild      kg/ha Bean Cotton Glory lebur Cassia sedge grass grass Oats Wheat Corn      Soybean Rice Sorghum       ##STR183##       2 7D,8G,6Y 4C,9G 10C 10C 2C,7G 8G 1C,4G 2C,8H 4G 3G 1C,5G 5H,7G 5G 7G       ##STR184##       2 3G,4C,6Y 2C,3H,6G 10C 2C,7G 2C,6G 2C,7G 6G 3C,7H 2G 2G 3C,6G 9C 2C,5G 3      C,7G       ##STR185##       2 3C,4G,6Y 2C,5G 7C 3C,7G 2C,7G 2G 4G 2H 0 0 2C 2H,6G 1C 0       ##STR186##       2 -- 9C 9C 9C 9C 5C 9C 9C 9C 9C 10C 9C 5C, 8G 7C       ##STR187##       2 -- 5C,9C 10C 10C 10C 8C 8C 9C 9C 9C 10C 3C,8G 5C,7G 5C,9G       ##STR188##       2 3C,8G,6Y -- 1C,9G 1C,7G 8H 9G 2C,8G 9H 0 0 2H,8G 2H,9G 2C,8G 9H       ##STR189##       2 8C,9G -- 9C 5C,8G 8C 7G 6G 5C,9H 2C,8G 3C,7G 7U,9G 9C 3C,8G 1U,8G       ##STR190##       2 9C 2C,2H,9G 2H,7G 1C,5G 5C,9G 1C,8G 10C 10C 2C,9G 2C,8G 2C,9G 1C,9G      5C,9G 2U,9G       ##STR191##       2 4S,3H,8G 3C,9G 10C 8G 2C,9G 1C,8G 5G 2C,9H 4G 6G 1C,9G 5C,9G 5C,9G    9      2C,G       ##STR192##       0.4 3S,3H,8G 2C,8G 10C 2C,7G 3C 8G 4G 1C,4H 0 0 2H,9G 9C 3C,9G 1C,9G       ##STR193##       2 9C 9C 10C 9C 9C 9C 9C 10C 9C 8C 9C 10C 9C 9C       ##STR194##       0.4 9C,9D 9C,9G 9C 10C 9C 9C 2C,8G 4C,9H 2C,7G 2C,7G 9C 10C 9C 9C       ##STR195##       0.4 9C 9C 10C 9C 9C 10C 9C 9C 5C,7G 8C 10C 9C 9C 9C       ##STR196##       0.4 9C 6C,9G 9C 9C 7C 10C 8C 10C 5C,5G 5C,5G 10C 2C,2H 6C,9G 9C       ##STR197##       2 8C 9C 10C 10C 9C 9C 9C 9C 9C 9C 9C 9C 9C 9C       ##STR198##       0.4 8C 9C 9C 10C 9C 8C 3C,8G 9C 9C 9C 9C 9C 9C 9C       ##STR199##       0.4 9D,9G 9C 10C 10C 9C 9C 10C 10C 9C 4C,8G 10C 5C,9G 9C 10C       ##STR200##       2/5 9C 7C9G 5C9G 1H 6C9G 2G 3G 1C5H 0 1C 5U9G 7C9G 1C6G 1C7G       ##STR201##       2/5 6C9G6Y 5C9G 6C9G 3C8G 5C8G 3U 3G 4C8H 0 0 3U9G 4C9G 7G 2C8G       ##STR202##       2/5 9D9G6C1 6C9G 6C9G 1C 1C5G 2G 1C2G 3C8H 1C 1C 2U9H 9C -- 1C7G       ##STR203##       2/5 9C 2H5C 1C6G 1C5G 5C8G 1C5G 1C8H 9C 1C 1C 9C 9G 4C7G 2C9G       ##STR204##       2/5 9C 5C8G 10C-- 5G 9C 4G 1C5G -- 1C4G 1C2G 9C 9C -- 2C8G       ##STR205##       2/5 5C9G6Y 9C-- 10C-- 2C8G 2C9G 2C8G 2G-- 2C9H 0-- 0-- 8H-- 5C8G 4C8G      6G--       ##STR206##       2/5 9D,9G 6C,9G 10C 3H,8G 5C,8G 0 1C 3C,9H 2C 0 4C,9G 5C,9G -- --       ##STR207##       2/5 3C,9G,6Y 5C,9G 9C 5C,9G 4C,8G 2G 2C,4G 5C,8H 2C 1C 9U,9C 9C 6C,9G      2C,8G       ##STR208##       2/5 9C 5C,8G 5C,9G 1C,3H,6F 5C,6G 6G 1C,6G 9C 1C,3G 4C,8H 10C 4C,8G      5C,8G 4U,8G       ##STR209##       2/5 2S,8G,6Y 5C,8G 10C 1C -- 0 2G 5G 0 1C 1C,5G 9C -- 4G       ##STR210##       2/5 2C,6Y 3C,5G 3C,8G 0 3C 2C 2G 2G 0 0 1C 5C,8G -- 0       ##STR211##       2/5 5C,9G 5C,8G 10C 2C,8G 9C 0 1C,3G 10C 1C,3G 1C,3G 5U,8G 6C,8G --      1C,8G       ##STR212##       2/5 9C 6C,9G 10C 1C,6F 6C,8G 1C,6G 6C,9G 9C 6C,8H 2U,4C,7G 10C 9G 6C,9G 4      U,8G       ##STR213##       2/5 8C 4G,2H,5G 2C,6G 4G,6F 3C,4H 0 1C 2C,7H 2C,4G 2C,6G 9C 2C,3H 5C,9G 1      C,9G       ##STR214##       2/5 8C 6C,9G 10C 10C 5C,7G 5G 4G 4C,9H 5C,8H 9C 10C 6C,9G 9C 2C,9G       ##STR215##       2/5 9C 9C 10C 10C 9C 5G 3C,7G 9C 9C 10C 10C 9C 10C 10C       ##STR216##       2/5 4C,9G,6Y 4C,7G 9C 2H 2C,8G 0 2G 2H 0 0 1C,4H 9C 1C,5G 2H       ##STR217##       2/5 5C,9G,6Y 5C,8G 9C 5G 2C,9G 3G 2G 2C,7H 1C 1C 8H 9C 2C,6G 3G       ##STR218##       2/5 2C,8D,9G 3C,7G 10C 8G -- 4G 1C 2C 0 0 8H 9C -- 3G       ##STR219##       2/5 8C 6C,9G 10C 6C,9G 5C,9G 2C,9G 0 10C 1C 2C,6G 9C 9C -- 2C,9G       ##STR220##       2 2C,4H 2H 5C,9G 2C,8G 1C,1H 3G 0 2G 1C 1C 7H 5H 2G 6G       ##STR221##       0.1 0 0 0 0 0 0 0 0 0 0 0 0 0 0       ##STR222##       0.1 4G,5F,2C 0 9G 5G 2G 0 0 0 0 0 0 5G 0 0       ##STR223##       0.4 9C 6C,9G 10C 4G 2C,7G 5G 2G 1C,8H 1C 1C 10C 1C,9G 1C,9G 1C,9G       ##STR224##       0.4 5C,6Y 3C,5G 4C,8G 2G -- 2G 2G 2G 0 0 0 9C -- 0       ##STR225##       0.4 2C 2C,7G 2C,5G 1C 5C 0 0 1C 0 0 1C 2C,6G 5G 1C       ##STR226##       0.4 4C,8G,6Y 4C,9G 5C,9G 3G 1C,5G 0 1C 1C,3G 0 0 6H 2C,8G 0 1C,5G       ##STR227##       2 5C,9G,6Y 2C,3H,9G 9C 2C,8G 1C,5G 1C,5G 1C 2C,8H 1C 1C 1U,9H 2C,9G      1C,7G 1C,9H       ##STR228##       0.4 3C,9G,6Y 2C,2H,9G 2C,9G 9G 1C 0 0 1H 0 0 1C,5H 2C,5G 5G 2C,8H        Pre-Emergence   Morning     Barnyard Wild       kg/ha Glory Cocklebur      Cassia Nutsedge Crabgrass Grass Oats Wheat Corn Soybean Rice Sorghum       ##STR229##       2 9G 8G 9G 10E 7G 8G 4G 5G 9H 8H 10E 9H       ##STR230##       2 9G 8G 9G 10E 8G 3C,9H 6G 8G9G 9H 9H 2C,9G       ##STR231##       2 8G 7G 4G 9G 3G 1C 0 3G 2C,4G 3H 6G 3G       ##STR232##       2 10E 8G 9G 10E 10E 9H 9C 9H 10E 9H 10E 9H       ##STR233##       2 9G 9C 9C 10E 10E 9H 3C,8G 9H 9H 9H 10E 9E       ##STR234##       2 9G 9G 8G 10E 3G 9H 6G 6G 2U,4G 6H 10E 9H       ##STR235##       2 9H 8G 8G 9G 6G 9H 2C,8G 9H 10E 9H 10E 9H       ##STR236##       2 9G 10E 10E 10E 10E 3C,9H 2C,9H 9H 10E 9H 10E 10C       ##STR237##       2 9G 7G 7G 10E 6G 2C,9H 5G 9G 10E 9G 10E 9G       ##STR238##       0.4 7G 6G 8G 9G 3G 1C,8G 3G 7G 9G 9G 10E 9G       ##STR239##       2 10E 9G 9G 10E 9H 9H 9G 9H 9G 9H 10E 9H       ##STR240##       0.4 9G 9G 9G 10E 9G 9H 9G 9G 9G 9H 10E 10E       ##STR241##       0.4 9C 9G 9G 5C,9G 7G 5C,9H 1C,5G 7G 9G 9H 10E 4C,9H       ##STR242##       0.4 9G 9G 5C,9G 10E 2C,5G 5C,9H 2C,6G 9H 10H 9H 10E 10H       ##STR243##       2 10E 9G 9G 10E 9G 10H 9H 9H 10E 9H 10E 10E       ##STR244##       0.4 10E 9G 9G 10E 10E 10H 9G 9H 10E 9H 10E 9H       ##STR245##       0.4 9G 9G 9G 10E 9E,9G 10H 2C, 9G 10H 10E 9H 10E 10H       ##STR246##       2/5 9G 2C9G 3C9G 4G 0 2C7H 0 0 1C9G 1C4H 1C5G 1C 8G       ##STR247##       2/5 9G 9G 9G 3G 5G 2C9H 0 0 9G 9H 5H 1C8G       ##STR248##       2/5 9H 9G 9G 2G 2G 4C8H 0 0 2C8G 9H 9H 1C8G       ##STR249##       2/5 9G 8G 8G 5G 1C 5C9H 1C 5G 9G 9H 5C9H 2C9H       ##STR250##       2/5 9G 8G 9G 9G 1C5G 1C9H 5G 1C8G 9G 9H 10E 1C9G       ##STR251##       2/5 9G 9G 9G 2G -- 8H 0 0 8G 9H 8H 6G       ##STR252##       2/5 2C,9G 9C 5C,9G 0 2G 9H 5G 5G 9G 7H 9H 2C,8H       ##STR253##       2/5 9G 9G 5C,9G 4G 3G 6H 7G 9H 5C,9G 5H,9G 10E 3C,9G       ##STR254##       2/5 9G 9G 5C,9G 2C,9G 2C,6G 5C,9G 2C,7G 1C,9H 10H 3C,8H 10E 2C,9H       ##STR255##       2/5 9G 8G 9G 0 2G 6G 0 2G 2C,8G 9H 1C,4G 4G       ##STR256##       2/5 7G 3G 5G 0 2G 0 0 0 3G 1C,1H 1C 1C,3G       ##STR257##       2/5 9G 7G 8G 4G 0 2C,9H 2G 2G 1U,9G 9H 10E 1C,9G       ##STR258##       2/5 9G 9G 3C,9G 1C,7G 3C,7G 5C,9H 2C,8G 1C,9G 9G 9H 10E 5C,9H       ##STR259##       2/5 5C 2H 2C,8G 0 2G 2C,8H 6G 9H 9G 1C,3H 10E 3C,9H       ##STR260##       2/5 9H 9G 2C,9G 3C,8G 3G 3C,9H 2C,9G 9G 9H 8H 10E 5C,9H       ##STR261##       2/5 9C 9G 9C 7G 2C,8G 3C,9H 3C,9G 1C,9G 3C,9G 9H 10E 10H       ##STR262##       2/5 8G 8G 9G 3G 3G 3G 0 0 4G 8H 6G 3G       ##STR263##       2/5 9G 8G 9G 3G 3G 7G 2G 2G 7G 9H 9H 6G       ##STR264##       2/5 9C 7G 8G 7G 0 7H 0 2G 1C,8G 9H 9H 8G       ##STR265##       2/5 9G 8G 9G 10E 0 2C,9H 2G 1C,9G 2C,9G 9H 10E 1C,9G       ##STR266##       2 10E 9H 9G 10E 5G 2C,8G 1C,6G 6G 2C,9G 9H 10E 2H,9G       ##STR267##       0.1 2G 0 0 0 0 0 0 0 0 2G 0 0       ##STR268##       0.1 5G 0 0 0 0 0 0 0 0 0 0 0       ##STR269##       0.4 9G 8G 8G 0 0 0 0 0 8H 5H 3G 3G       ##STR270##       0.4 8G 2G 5G 0 0 0 0 0 1C,5G 2C,5H 1C 1C       ##STR271##       0.4 0 0 0 0 0 0 0 0 0 0 0 0       ##STR272##       0.4 9G 8G 1C,9G 0 0 1H -- 0 1C,8G 1C 1C 2G       ##STR273##       2 9G 9H 2C,9G 8G 1H 9H 1C,6G 7G 1U,9G 8H 10E 1C,9H       ##STR274##       0.4 8G 9H 9G 2G 0 1C,6G 1H 2G 1C,9G 2C 9H 1C,7G

Test Procedure B

Two bulb pans were filled with fertilized and limed Fallsington silt loam soil. One pan was planted with seeds of corn, sorghum, Kentucky bluegrass and several grassy weeds. The other pan was planted with seeds of cotton and soybeans, purple nutsedge tubers (Cyperus rotundus), and seeds of several broadleaf weeds. Seeds of the following grassy and broadleaf weeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense), giant foxtail (Setaria faberii), dallisgrass (Paspalum dilatatum), cheatgrass (Bromus secalinus), mustard (Brassica arvenis), cocklebur (Xanthium pennsylvanicum), pigweed (Amaranthus retroflexus), morningglory (Ipomoea hederacea), cassia (Cassia tora), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A smaller pot was also filled with prepared soil and planted with rice and wheat seeds. Another small pot was planted with seeds of sugarbeets. The above four containers were treated preemergence with nonphytotoxic solvent solutions of the compound of Table 10 (i.e., solutions of compounds were sprayed on the soil surface before seed germination). Duplicates of the above-described seeded containers were prepared without treatment and used as controls.

Twenty-eight days after treatment, the treated and control plants were evaluated and the data recorded as set forth in Table 10. Note that the data indicate that certain compounds of this invention are useful for weed control in crops such as soybeans and wheat.

    TABLE 10       PRE-EMERGENCE ON FALLSINGTON SILT FOAM                 Ky.       Rate Crab- Barnyard- Sor- Wild Johnson- Dallis-      Giant Blue- Cheat- Sugar-   Cock-  kg/ha grass grass ghum Oats grass      grass Foxtail grass grass beets Corn Mustard lebur       ##STR275##       1/161/4 10C10C 8G,8C10C 9G,9C10C 4G,3C8G,5C 8G,5C10C 8G,5C10C 8G,6C10C      10C10C 10C10C 10C10C 8G,8H10C 10C10C 2G7G       ##STR276##       1/161/4 5G7G 8G,9C10C 7G,8C10C 4G8G,5C 8G,5C9G,5C 7G8G,5C 7G,4C9G,8C      6G,3C8G,8C 8G,3C8G,3C 10C10C 8G,8H9G,9H 10C10C 4G8G,5H       ##STR277##       1/161/4 03G 4G6G 3G7G 2G4G 07G 00 04G 05G 05G 8G,5C9G,8C 3G7G ---- 6G5G       ##STR278##       1/161/4 05G 8G,8G10C 8G,8H10C 5G,3H5G 7G,5H10C 4G10E 6G10C 8G10E      8C,5H10C 4G8G,5H 7G,5H10C 8G10C 00          Rate             kg/ha Pigweed Nutsedge Cotton Morningglory Cassia      Teaweed Velvetleaf Jimsonweed Soybean Rice Wheat       ##STR279##       1/161/4  10E10E 4G9G 5G,3H7G,5H 5G8G 5G8G,9C 5G,3C9G,8C 5G9G,9C 5G9G,9C 2      G8G,5H 9G,9C10C 7G,4C10C       ##STR280##       1/161/4 10E10E 10E10E 7G7G 7G8G,3H 6G8G,5C 6G,3C8G,8C 6G10C 6G10C      7G,5H8G,5H 9G,9C10C 4G7G,3C       ##STR281##       1/161/4 ----  7G5G ---- 5G5G ---- ---- ---- 3G5G 5G7G,5H 7G10C 00       ##STR282##       1/161/4 10C10C 00 ---- 03G 08G 03G ---- 04G 02G 7G,5H10C 5G7G

TEST PROCEDURE C

Pots filled with Fallsington silt loam were planted to soybeans, cotton, alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), cassia (Cassia tora), morningglory (Ipomoea spp.), jimsonweed (Datura stramonium), cocklebur (Xanthium pennsylvanicum), crabgrass (Digitaria spp.), nutsedge (Cyperus rotunda), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii), and wild oats (Avena fatua). Approximately 21/2 weeks after planting, the young plants and the soil around them were sprayed overall with the compounds of Table 11 dissolved in a nonphytotoxic solvent. Other groups of all the same weed and crop plants were sprayed with the same nonphytotoxic solvent so as to provide control plants. Fourteen days after treatment, all treated plants were compared with the nonphytotoxic solvent controls and visually rated for response to treatment to give the data presented in Table 11. The data indicate that several of the compounds tested by this procedure are useful for the post-emergence control of weeds in wheat.

    TABLE 11       OVER THE TOP SOIL/FOLIAGE TREATMENT          Vel-    Morn-  Jim-      Barn-     Rate Soy- vet- Ses- Cas- Cot-      ing- Al- son- Cock-  Crab-  Nut- yard-  Giant Wild Sor- kg/ha beans leaf      bania sia ton glory falfa weed lebur Corn grass Rice sedge grass Wheat      Foxtail Oats ghum       ##STR283##       1/161/4 10C10C 10G,7C10G,9C 10C10C  5F,3C10G,7C 8G,5C10G,7C 5C,5C10C      10G,7C10G,9C 5G,3C10C 3G5G,3C 10G,9C10G, 9C 10G7C10G,5C 10G,4C10G,6C      4G7G 10C10G,6C 10G,4C10G,2C 10G,3C10G,6C 10G,3C10G,6C 10G,8C10G,6C       ##STR284##       1/161/4 10C10C 10C10C 10C10C 10G,5C10G,6C 10G,3C8G,5C 9G,3C10C 10G, 9C10      G,9C 10C10C 10G,7C10G,7C 10G,7C10G,9C 10G,6C10G,9C 10G,7C7G,4C 7G7G      10C10G,7C 6G7G,2C 10G,5C10G,3C 10G,3C8G,2C 10G,5C10G,9C       ##STR285##       1/161/4 8G,2C10G,4C 05G 05G,2C 3H3G,5H 3G3G 06G 07G 07G,4C 03G,2C      3G,2H8G,5H 03G 0 0 00 5G8G 00 03G 00 5G,3H7G,3H       ##STR286##       1/161/4 10G,6C10G,7C 5G,2C10G,5H 10G,5C10G,8C 10G,4C10G,6C 8G,2C10C      6G8G,2C 4G10G,4C 7G,2C9G,3H 3G5G 7G8G 05G 10G10G,2C 00 10G,10G,4C 07G      5G10G,3C 08G,3C 10G10G,3C       ##STR287##       1/161/4 2G,3B5G,3B 2G5G 10G,2C10G,5G 05G 4G6G 00 5G5G 2G4G 00 10G,3C10G,4      C 3G4G 7G5G,2C 03G 8G,3C10G,4C 8G,3C10G,3C 6G10G 6G10G,3C 8G,2C10G,3C 

What is claimed is:
 1. A compound selected from ##STR288## wherein R is ##STR289## R₁ and R₂ are independently H or CH₃ ; R₄ is Cl, Br, F, NO₂, CH₃, OCH₃, CF₃ or R₃ S(O)_(n), where R₃ is C₁ -C₆ alkyl or C₃ -C₄ alkenyl;R₅ is H, Cl, Br, F, CH₃ or --OCH₃ ; n is 0, 1 or 2; W is O or S; X is CH₃ or --OCH₃ ; Y is C₃ -C₄ alkyl; C₂ -C₄ alkyl substituted with CH₃ O; C₂ -C₄ alkyl substituted with 1-3 atoms of Cl, Br or F; C₁ -C₄ alkyl substituted with C₂ H₅ O, CN, CO₂ H, CO₂ CH₃ or CO₂ C₂ H₅ ; CH₂ F; CH₂ Cl; CH₂ Br; C₂ -C₄ alkenyl; C₂ -C₄ alkynyl; SCN: N₃ ; A(CH₂)_(m) A₁ R₇ ; where m is 2 or 3; R₇ is C₁ -C₃ alkyl; A is O or S; and A₁ is O or S(O)_(n) ; ##STR290## where A₂ and W₁ are independently O or S, and R₁₅ is C₁ -C₃ alkyl, optionally substituted with 1-3 F, Cl or Br, or R₁₅ is N(CH₃)OCH₃ or NR₈ R₉ ; ##STR291## where L is N(CH₃)OCH₃ or NR₈ R₉, where R₈ and R₉ are independently H, CH₃ or C₂ H₅, or L is OR₁₀ where R₁₀ is H or C₁ -C₄ alkyl; NR₁₁ R₁₂ where R₁₁ is H or CH₃ and R₁₂ is C₃ -CH₄ alkenyl, C₂ -C₃ alkyl substituted with OCH₃ or OC₂ H₅, cyclopropyl or C₁ -C₂ alkyl substituted with CN, CO₂ CH₃ or CO₂ C₂ H₅ ; OR₁₃ where R₁₃ is C₄ -C₆ alkyl, C₁ -C₄ cyanoalkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, ##STR292## or C₂ -C₄ alkyl substituted with 1-3 atoms of F, Cl or Br; SR₁₄ where R₁₄ is C₁ -C₂ cyanoalkyl, allyl or propargyl; and Z is CH and its agriculturally suitable salts;with the proviso that: (1) (a) when Y is OCH₂ CF₃ ; (b) when Y is A--CH₂)_(m) OR₇ and R₇ is CH₃ or CH₃ CH₂ ;(c) when Y is ##STR293## and L is CH₃ O or CH₃ CH₂ O; or (d) when Y is ##STR294## and R₁₅ is CH₃ or CH₃ CH₂, then in a, b, c or d, R₄ must be R₃ S(O)_(n), where R₃ is other than CH₃ ; and (2) when either or both of R₁ and R₂ is CH₃, Y cannot be OCH₂ CH₂ OCH₃.
 2. A compound of claim 1 whereinY is C₁ -C₄ alkyl substituted with CN, CO₂ CH₃, or CO₂ C₂ H₅ ; C₂ -C₄ alkyenyl; C₂ -C₄ alkynyl; SCN; N₃ ; A(CH₂)_(m) A₁ R₇, where m is 2 or 3, R₇ is C₁ -C₃ alkyl and A₁ is O or S(O)_(n) ; ##STR295## where A is O or S, and L is N(CH₃)OCH₃ or NR₈ R₉, where R₈ and R₉ are independently H, CH₃ or C₂ H₅, or L is OR₁₀ where R₁₀ is C₁ -C₄ alkyl; NR₁₁ R₁₂ where R₁₁ is H or CH₃ and R₁₂ is C₃ -C₄ alkenyl, C₂ -C₃ alkyl substituted with OCH₃ or OC₂ H₅, or C₁ -C₂ alkyl substituted with CN, CO₂ CH₃ or CO₂ C₂ H₅ ; OR₁₃ where R₁₃ is C₁ -C₄ cyanoalkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, ##STR296## or C₂ -C₄ alkyl substituted with 1-3 atoms of F, Cl or Br; SR₁₄ where R₁₄ is C₁ -C₂ cyanoalkyl, allyl or propargyl.
 3. A compound of claim 2 wherein R₁ and R₂ are H and W is O.
 4. A compound of claim 3 wherein Y is AR₁₆ where R₁₆ is CH₂ CF₃, CH₂ CH₂ OR₁₇, CH(CH₃)CO₂ R₁₇, (CH₂)₃ OR₁₇ or CH₂ CH₂ CO₂ R₁₇, where A is O or S and R₁₇ is CH₃, --C₂ H₅ or i--C₃ H₇.
 5. A compound of claim 4 wherein A is O and R₁₆ is other than CH₂ CH₂ CO₂ R₁₇.
 6. A compound of claim 5 wherein R is ##STR297##
 7. A compound of claim 6 wherein R₅ is H or Cl.
 8. A compound of claim 7 wherein R₄ is Cl or NO₂.
 9. A compound of claim 8 wherein R₅ is H.
 10. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 1 and at least one of the following: surfactant, solid or liquid diluent.
 11. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 2 and at least one of the following: surfactant, solid or liquid diluent.
 12. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 3 and at least one of the following: surfactant, solid or liquid diluent.
 13. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 4 and at least one of the following: surfactant, solid or liquid diluent.
 14. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 5 and at least one of the following: surfactant, solid or liquid diluent.
 15. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 6 and at least one of the following: surfactant, solid or liquid diluent.
 16. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 7 and at least one of the following: surfactant, solid or liquid diluent.
 17. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 8 and at least one of the following: surfactant, solid or liquid diluent.
 18. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 9 and at least one of the following: surfactant, solid or liquid diluent.
 19. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 1. 20. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 2. 21. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 3. 22. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 4. 23. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 5. 24. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 6. 25. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 7. 26. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 8. 27. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 9. 